Detergent compositions



United States Patent Ofitice 3,349,038 Patented Oct. 24, 1967 3,349,038 DETERGENT COMPOSITIONS Edwin B. Michaels, Stamford, and Clayton A. Wetmore,

Norwallr, Conn., assignors to Stamford Chemical Industries, Inc., fincinnati, Ohio, a corporation of Ghio N Drawing. Filed Apr. 24, 1962, Ser. No. 189,699 6 Claims. (Cl. 252-161) The present invention relates to novel drycleaning detergent compositions. More particularly, it relates to a detergent mixture comprising oil-soluble petroleum sulfonates and water-soluble alkyl aryl sulfonates. Still more particularly, the invention is concerned with an improved detergent additive for use in a drycleaning solvent capable of exhibiting both increased detersiveness and increased water-binding properties.

The use of oil-soluble petroleum sulfonates as a drycleaning soap additive to a charge system" has gained acceptance in recent years. Although the soaps detersiveness is not exceptional by any standard in the art, the soap can be reused again and again because it is not adsorbed by the filter medium as the charged solvent is passed through the filter to remove lint and other impurities due to the drycleaning operation. Thus as a detergent, oil-soluble petroleum sulfonate is satisfactory. However, it suffers a serious drawback in that it has no capacity to bind water in the charged solvent system. If water is not bound, free water in the system can irreparably damage a garment to be cleaned. To impart water binding properties to oil-soluble petroleum sulfonate soap-solvent systems, non-ionics have been added thereto. Unfortunately, the improvement in water binding results in substantially decreased detersiveness, particularly with respect to redeposition of soil during the cleaning operation. This has sharply limited the use of oil-soluble petroleum sulfonates as an additive to a drycleaning solvent.

It is a principal object of the invention to avoid the drawbacks of the prior practice and to provide a deter gent additive to a drycleaning solvent which impart both increased detersiveness and water-binding properties thereto. It is a further object of the invention to provide a detergent mixture comprising an oil-soluble petroleum sulfonate in major amounts and a water-soluble anionic detergent in minor amounts to increase both detersiveness and water-binding properties in a drycleaning solvent. Other objects and advantages can be readily ascertained from the following detailed description.

It has been unexpectedly found that the foregoing objects can be met in a straight-forward manner by incorporating a water-soluble anionic into an oil-soluble petroleum sulfonate. Thus, a mixture comprising a major amount of (a) an oil-soluble petroleum sulfonate having an average molecular weight from about 425 to about 465 and (b) an alkyl aryl sulfonate of average molecular weight between about 200 and 350 as a detergent additive to a solvent system, surprisingly markedly enhances both water-binding and detersive properties of the over-all detergent mixture. Small quantities of the latter mixture when added to a drycleaning solvent are completely compatible therein. Concentrations of the mixture from about 0.2% to about based on the drycleaning solvent, yield optimum beneficial results with respect to both detersiveness and water-binding properties.

The oil-soluble petroleum sulfonate soaps which are employed herein are commercially available. Suitable oilsoluble sulfonates having average molecular weights of above 400 are sold under various tradenames such as Shell Pale OS and Sonneborn Petronate K. These are viscous monofunctional sulfonates of a long chain parafiinic radical attached to an aromatic-naphthenic nucleus having the empirical structure:

Where Me is an alkali metal such as sodium, potassium or lithium and n is integer from 25 to about 30. The average molecular weight of these sulfonates is about 450. Another type is the utilization of slightly lower average molecular weight oil-soluble petroleum sulfonates in the range of about 425 sold under the tradename Shell 425. In practice, equal parts by weight of Shell 425 and Shell Pale OS can advantageously be admixed. Similarly, varying amounts of oil-soluble petroleum sulfonates such as, for instance, a composition comprising between 25% and 33% petroleum sulfonate of molecular Weight between about 370 and 425, between 25% and 66% petroleum sulfonate of molecular Weight between 425 and 470 and between 0% and 33% petroleum sulfonate of molecular weight between about 470 and 500, can be employed. Although the molecular weight of oilsoluble petroleum sulfonate can be widely varied, the principal requirement is that the average molecular weight of the sulfonate soap utilized be maintained between about 425 and 465.

The oil-soluble petroleum sulfonates which are highly viscous material can be conveniently diluted so that they can be more easily handled. Inert solvents, such as deodorized kerosene, naphtha, benzene, are contemplated. The solvents may additionally be combined, if desired, with small amounts of an aliphatic alcohol, such as pentanol, methyl isobutyl carbinol, hexylene glycol and the like.

To impart exceptional water-binding properties to the oil-soluble petroleum sulfonate as well as improving its detersiveness, small amounts, usually between about 1% and 8% of a water soluble alkyl aryl sulfonate, based on the weight of the oil-soluble petroleum sulfonate, are added thereto. In general, any alkyl aryl sulfonate having molecular weights between about 200 and 350 or mixtures of the same, such as sodium dodecyl benzene sulfonate or sodium xylene sulfonate can be advantageously employed. In the event an alkyl aryl sulfonate having a molecular weight in the range of about 200 and 250 is employed, it is a convenient practice to use from about 1% to about 3% of the alkyl aryl sulfonate, based on the weight of the petroleum sulfonate. In like manner, when employing alkyl aryl sulfonate of molecular weights above 250, it is a good practice to employ from 2% to 8% based on the weight of the petroleum sulfonate.

As stated previously, from about 0.2% to 5% of the over-all detergent mixture comprising from 99% to 92% oil-soluble petroleum sulfonates having an average molecular weight between 425 and 465 and from about 1% to about 8% of a water-soluble alkyl aryl sulfonate of molecular weight ranging from about 200 to about 350, is added to any commercially available drycleaning solvent. However, prior to the incorporation of the over-all detergent composition into the solvent, about 1% to 5% of water based on the overall weight of the additive mixture is conveniently added so that the mixture can be more readily handled.

Illustrative drycleaning solvents are: Stoddards solvent, petroleum ether, perchloroethylene, trichloroethylene and the like.

The invention will be further described and illustrated by the following examples which demonstrate the application of the principles above defined to illustrate detergent additives to drycleaning solvents for effecting increased detersiveness and water-binding of the additives in the solvents. It will be understood that the invention in its broader aspects is not deemed limited to the detailed quantities and procedures illustrated in these examples and unless otherwise stated, the parts are by weight.

Examples 1-8 Enhanced detersive properties of the compositions illustrated in the table below are determined in the conventional manner involving the use of a launderometer In each of the examples below, the detergent composition is prepared by admixing the following:

Percent Sodium, petroleum sulfonate (aver. mol. weight,

as described in the AATCC yearbook for 1955 and at 5 S if ----.-g page 55 and following et seq. In a typical run a standard Petro sum Ona e (aver' mo wag 39 soiled swatch and Stainless steel balls together with the D d E 19 drycleaning solvent, petroleum ether, containing 2% by 3 weight of the detergent additive, are added to a launderat y 150 my car mo ometer jar. After a twenty minute wash cycle, the washed The detergent composition hereinafter designated as A swatchis removed from the jar, and dried to remove the is incorporated into either petroleum ether (Pet) solsolvent. Reflectance readings before and after washing of vent or perchloroethylene (Pere) solvent in an amount the soiled and unsoiled swatches are taken andrccorded equal to 2% by weight of the solvent and tested with the in percent detergency and percent redeposition, typical cotton and wool swatches having the initial rerespectively. In the illustrative examples below, the initlal flectance readings above mentioned. The results are noted reflectance readings of the cotton and wool swatches used fte designated amounts of di d d b are: 103 and 92, respectively; the soiled swatches for cotsulfonate, hereinafter designated as NRSF, have been ton and wool are and 28, respectively. Percent deteradded in separate examples and in amounts set forth in gency is determined by subtracting the reflectance readlng Table 1 below. The results are presented therein.

TABLE 1 Cotton Wool Percent S.S.R. Ex. Composition Percent Percent Percent Percent V.W.T.V.

Detergency Redeposition Detergeney Redepositiou Pet. Perc. Pet. Pere. Pet. Perc. Pet. Pere. Pet. Pere.

1 CompositionA 178 20.5 5 8 3.9 42.2 50 10.8 10.8 60 0.19 2 Oil 80121551? Petroleum Sultanate (avg. nrol. 20.3 24.6 6.5 3.9 57.8 47.7 5.4 10.8 40 80 0.32

wt.= 3 Oil 801111111; Petroleum Sulionate (avg. moi. 20.3 31.4 3.9 1.9 54.5 57.4 9.8 4.4 60. 100 0.19

\vt.= 25 4 Aplus 2% NRSF plus 2% H 0. 24.6 30.1 2.9 3.9 65.5 59.5 4.4 5.5 100 2.4 5 Aplus5%NRSFplus5%H O 24.5 35.6 0 1.0 70.5 61.0 10.8 8.7 100 1.8 6 A plus 8% NRsF plus 5%11 0 20.5 24.6 1.94 2.9 70.5 70.5 8.7 8.7 40 60 0.28 7 Alguswlyb Sodium Xylene Sulfonate plus 33.0 42.5 2.9 1.9 62.5 59.5 0 1.1 100 100 0.97

, ater.

s Aplu s 10% Non-ionic 21.9 24.6 9.7 34.0 26.4 53.1 60.9 13.1 100 100 0.97

11 Sweet Stain Removal.

b V.W.T.V. means Visual Water Tolerance Value which is defined above in the equation for the definition of water tolerance.

NRSF means Sodium dodecyl benzene sulionate;

d Non-ionic used is nonylpheuoxypoly(ethyleneoxy) ethanol, consisting or 63% combined ethylene oxide on weight of nonyphenol.

of the soiled swatch and dividing this difference by the difference between the initial unsoiled swatch reflectance reading and the soiled reflectance reading, multiplied by 100. Thus, for instance, the percent detergency for cotton is:

R 0 1O0 l03b0 Where R is the reflectance reading of the soiled swatch after drycleaning, whereas the percent redeposition for cotton is similarly represented by the formula:

IOBR XIOO 103 where R is the reflectance reading of unsoiled swatches after drycleaning. In the examples below the percent detergency and percent redeposition are each deter-. mined in two solvent media, namely, petroleum ether (Pet.) and perchloroethylene (Perc.).

Water binding test procedure is conducted in each of the examples below as follows:

The water tolerance value of an oil soluble detergent is a measurement of the. amount of water that the detergent will. hold or otherwise dissolve in solvent such as petroleum ether or perchloroethylene. Water tolerance value herein is obtained by visual measurements in the formula below by adding water to a known amount of detergent dissolved in solvent until the solution shows a definite cloudiness:

Amt. of Water (in grams) 1 V.W.T.V. means Visual Water Tolerance Value.

465 and a minor amount of a water-soluble alkyl aryl sulfonate having a molecular weight from about 200 to about 350, said alkyl aryl 1% but not exceeding 8% weight.

2. The composition according to claim 1 in which the sodium xylene sulfonate present in amounts equal to from about 1% to about 3% by weight of the oil-soluble petroleum .sulfonate.

3. The composition according to claim 1 in which the water-soluble alkyl aryl sulfonate is sodium dodecyl benzene sulfonate present in amounts equal to from about 2% to about 8% by weight of the oil-soluble petroleum sulfonate.

4. A detergent-charged drycleaning solvent which consists essentially of: a major amount of a drycleaning solvent and a minor amount between 0.2% and 5% of the detergent composition defined in claim 1 above.

5. A detergent-charged drycleaning solvent of claim 4 in which the solvent is petroleum ether.

of the oil-soluble sulfonate by 6. A detergent-charged drycleaning solvent of claim4 in which the solvent is perchloroethylene.

(References on following page) sulfonate being present from.

5 6 References Cited 2,717,824 9/1955 Avery 252-89 X UNITED STATES PATENTS 2,859,182 11/1958 Carroll 252137 g; g if LEON D. ROSDOL, Primary Examiner.

11 1945 Fl 252 161 5 JULIUS GREENWALD, ALBERT T. MEYERS,

8/ 1951 Rapier 252-161 X Examiners.

9/1951 Irwin 1 W. E. SCHULZ, Assistant Examlner. 

1. A DETERGENT COMPOSITION SUITABLE FOR USE IN CHARGING A DRYCLEANING SOLVENT WHICH CONSISTS ESSENTIALLY OF: A MAJOR AMOUNT OF AN OIL-SOLUBLE PETROLEUM SULFONATE OF AVERAGE MOLECULAR WEIGHT BETWEEN ABOUT 425 AND ABOUT 465 AND A MINOR AMOUNT OF A WATER-SOLUBLE ALKYL ARYL SULFONATE HAVING A MOLECULAR WEIGHT FROM ABOUT 200 TO ABOUT 350, SAID ALKYL ARYL SULFONATE BEING PRESENT FROM 1% BUT NOT EXCEEDING 8% OF THE OIL-SOLUBLE SULFONATE BY WEIGHT. 